(2R,3R,6S,8S)-(+)-1,8-Bis<(4'-bromobenzoyl)oxy>-2-methyl-3,6-epoxyundecane | 152518-61-1

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: (2R,3R,6S,8S)-(+)-1,8-Bis<(4'-bromobenzoyl)oxy>-2-methyl-3,6-epoxyundecane
• 英文别名: (2R,3R,6S,8S)-1,8-bis(4-bromobenzoyloxy)-3,6-epoxy-2-methylundecane；[(2R)-2-[(2R,5S)-5-[(2S)-2-(4-bromobenzoyl)oxypentyl]oxolan-2-yl]propyl] 4-bromobenzoate
• CAS: 152518-61-1
• 化学式: C₂₆H₃₀Br₂O₅
• 分子量: 582.329
• InChiKey: ZAKLFBZHFQAANA-XECWOPBBSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  7.6
• 重原子数：
  33
• 可旋转键数：
  12
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.46
• 拓扑面积：
  61.8
• 氢给体数：
  0
• 氢受体数：
  5

反应信息

• 作为产物：
  描述：

  methyl (2S,3R,6S,8S)-3,6-epoxy-8-hydroxy-2-methylundecanoate 在 4-二甲氨基吡啶 、 lithium aluminium tetrahydride 、 三乙胺 作用下， 以 乙醚 、 二氯甲烷 为溶剂， 反应 12.5h， 生成 (2R,3R,6S,8S)-(+)-1,8-Bis<(4'-bromobenzoyl)oxy>-2-methyl-3,6-epoxyundecane
  参考文献：
  名称：

  Syntheses of the Lower Portions of the Pamamycins from .gamma.-(Silyloxy)allenes Using Stereoselective Cyclization, Reduction, and Aldehyde Addition Methodologies

  摘要：

  The pamamycins are a group of homologous macrodiolides produced by Streptomyces alboniger and Streptomyces aurantiacus JA 4570 which are remarkable for their autoregulatory, antifungal, antibacterial, and anion-transfering activities. The syntheses of the C-1'-C-11' (''lower'') portions of pamamycin-607, pamamycin-649A, pamamycin-635A, pamamycin-649B, and pamamycin-635B as the methyl esters 8 and 10-12 are reported. The C-9'-C-11', portions of these esters were introduced by chelation-controlled allylations of C-8' aldehyde intermediates derived from the C-8' alcohols 9 (whose synthesis has been previously reported) and 13-15 using allyltrimethylsilane in the presence of titanium(IV) chloride. The alcohols 13-15 were synthesized via cis selective cyclizations of the trimethylsilyl ether derivatives of the nonracemic gamma-hydroxy allenes 24, 30, and 31 using a one-pot oxymercuration/transpalladation/methoxycarbonylation reaction followed by a chelation-controlled conjugate reduction of the resulting acrylate intermediates. The gamma-hydroxy allene 24 was synthesized via an enzymatic resolution of the gamma-acetoxy allene 20, and the gamma-hydroxy allenes 30 and 31 were synthesized by asymmetric aldol reactions. During the syntheses of the products 14 and 15, chemoselective hydrolyses and reduction reactions were employed in order to differentiate a C-8' carboxyl group from the C-1' carboxyl group. Starting from simple allenyl alcohol starting materials, overall yields from 2% (in 14 steps, for 10) to 14% (in 9 steps, for 12) were observed for the production of the C-1'-C-11' portions of the pamamycins.

  DOI：

  10.1021/jo00091a037

文献信息

• Total syntheses of pamamycin 607 and methyl nonactate: stereoselective cyclisation of homoallylic alcohols that had been prepared with remote stereocontrol using allylstannanes
  作者：Olivier Germay、Naresh Kumar、Christopher G. Moore、Eric J. Thomas

  DOI：10.1039/c2ob26801a

  日期：——

  then replaced by an N-(tert-butoxycarbonyl) group and O-debenzylation and oxidation gave the carboxylic acid 70 that corresponds to the C(1)–C(18) fragment of pamamycin 607 (1). Similar chemistry was used to prepare the C(1′)–C(11′) fragment 89 of the pamamycin, except that in this case the configuration of the secondary alcohol introduced by the allylstannane reaction had to be inverted using a Mitsunobu

  发现在路易斯酸存在下，使用苯基硒烯基氯或邻苯二甲酰亚胺，由氯化锡（IV）介导的（Z）-均烯丙基醇的环化反应，然后还原性去除苯基硒烯基，可得到具有优异立体控制的2,5-顺式-二取代四氢呋喃。 。使用该程序，通过锡（IV）立体选择性地制备了（2 S，4 S，8 R，6 Z）-9-苄氧基-2-叔丁基二苯基甲硅烷基氧基-8-甲基非-6-烯-4-醇（11））之间的氯化物促进反应（R）-5-苄氧基-4-甲基戊-2-烯基（三丁基）锡烷（3）和（S）-3-叔丁基二苯基甲硅烷基氧基丁醛（10），得到（2 S，3 R，6 S，8 S）-1脱硒后的-苄氧基-8-叔丁基二苯基甲硅烷氧基-3，6-环氧-2-甲基壬烷（13）。将该四氢呋喃选择性地脱保护，氧化和酯化，得到非乳酸甲酯（2）。已经建立了2，5-顺式-二取代的四氢呋喃的这种合成，将其用于完成帕马霉素607（1）的合成。（2 S，3 R从（R）立体选择性地制备，6S，8R）-1-苄氧基-8-
• Synthesis of the C1′–C11′ portion of pamamycin-607 via a stereoselective oxymercuration of a gamma—silyloxyallene and a stereospecific magnesium—methanol reduction
  作者：Robert D. Walkup、Gyoosoon Park

  DOI：10.1016/s0040-4039(00)80798-4

  日期：1988.1

  The C1′–C11′ portion of the antibiotic pamamycin-607, a novel homologue and C2-epimer of nonactic acid, was synthesized in six steps from 4,5-hexadien-1-ol via a novel -selective oxymercuration/transpalladation/methoxycarboxylation of a γ-silyloxyallene and a -selective reduction of a 2-(2-tetrahydrofuranyl)acrylate using magnesium in methanol. Spectroscopic properties of a derivative of the synthetic

  的C 1'〜C 11'的抗生素pamamycin-607，一种新颖的同系物和C的部分2 nonactic酸差向异构体，在六个步骤通过一种新颖的合成由4,5-己二烯-1-醇-选择性oxymercuration /使用甲醇中的镁，将γ-甲硅烷基氧丙烯烯进行palpalpalation /甲氧基羧化反应，并选择性地还原2-（2-四氢呋喃基）丙烯酸酯。合成℃的衍生物的光谱性质1' -C 11'部分匹配的材料从天然产物衍生的。
• WALKUP, ROBERT D.;PARK, GYOOSOON, TETRAHEDRON LETT., 29,(1988) N 43, C. 5505-5508
  作者：WALKUP, ROBERT D.、PARK, GYOOSOON

  DOI：——

  日期：——
• Syntheses of the Lower Portions of the Pamamycins from .gamma.-(Silyloxy)allenes Using Stereoselective Cyclization, Reduction, and Aldehyde Addition Methodologies
  作者：Robert D. Walkup、Sang Woong Kim

  DOI：10.1021/jo00091a037

  日期：1994.6

  The pamamycins are a group of homologous macrodiolides produced by Streptomyces alboniger and Streptomyces aurantiacus JA 4570 which are remarkable for their autoregulatory, antifungal, antibacterial, and anion-transfering activities. The syntheses of the C-1'-C-11' (''lower'') portions of pamamycin-607, pamamycin-649A, pamamycin-635A, pamamycin-649B, and pamamycin-635B as the methyl esters 8 and 10-12 are reported. The C-9'-C-11', portions of these esters were introduced by chelation-controlled allylations of C-8' aldehyde intermediates derived from the C-8' alcohols 9 (whose synthesis has been previously reported) and 13-15 using allyltrimethylsilane in the presence of titanium(IV) chloride. The alcohols 13-15 were synthesized via cis selective cyclizations of the trimethylsilyl ether derivatives of the nonracemic gamma-hydroxy allenes 24, 30, and 31 using a one-pot oxymercuration/transpalladation/methoxycarbonylation reaction followed by a chelation-controlled conjugate reduction of the resulting acrylate intermediates. The gamma-hydroxy allene 24 was synthesized via an enzymatic resolution of the gamma-acetoxy allene 20, and the gamma-hydroxy allenes 30 and 31 were synthesized by asymmetric aldol reactions. During the syntheses of the products 14 and 15, chemoselective hydrolyses and reduction reactions were employed in order to differentiate a C-8' carboxyl group from the C-1' carboxyl group. Starting from simple allenyl alcohol starting materials, overall yields from 2% (in 14 steps, for 10) to 14% (in 9 steps, for 12) were observed for the production of the C-1'-C-11' portions of the pamamycins.